CN107321295B - Bell type structure Fe @ SiO2Composite microsphere, preparation method and application thereof - Google Patents
Bell type structure Fe @ SiO2Composite microsphere, preparation method and application thereof Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 141
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 140
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 106
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 102
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 102
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 102
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 102
- 239000002131 composite material Substances 0.000 claims abstract description 94
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 27
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 26
- 238000013329 compounding Methods 0.000 claims abstract description 22
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000011258 core-shell material Substances 0.000 claims abstract description 16
- 238000001179 sorption measurement Methods 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 9
- UUYKGYZJARXSGB-UHFFFAOYSA-N ethanol;ethoxy(trihydroxy)silane Chemical compound CCO.CCO[Si](O)(O)O UUYKGYZJARXSGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 238000007885 magnetic separation Methods 0.000 claims description 8
- 229910001385 heavy metal Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000010907 mechanical stirring Methods 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 63
- 239000011651 chromium Substances 0.000 description 28
- 238000001035 drying Methods 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- 238000001816 cooling Methods 0.000 description 12
- 239000011257 shell material Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000003673 groundwater Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 238000004627 transmission electron microscopy Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002077 nanosphere Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
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- 238000001000 micrograph Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000007771 core particle Substances 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
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- 238000005067 remediation Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000010420 shell particle Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 206010028400 Mutagenic effect Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000000711 cancerogenic effect Effects 0.000 description 1
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- 231100000243 mutagenic effect Toxicity 0.000 description 1
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- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
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- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28009—Magnetic properties
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
The invention belongs to the field of environment nano materials, and particularly relates to a bell-shaped structure Fe @ SiO2The preparation method of the composite microspheres comprises the following steps of firstly, adding ferric trichloride into water for dissolving, adding hydrochloric acid for uniformly stirring, transferring into a mechanical stirring reaction kettle, and carrying out hydrothermal reaction for 12-24 h at the temperature of 100-160 ℃ to obtain α -Fe2O3Step two, α -Fe prepared in the step one2O3Dispersing the nano microspheres into 20-98 vol% ethanol according to the solid-to-liquid ratio of 1 g: 60 ml-1 g: 120ml, adding ammonia water, stirring uniformly, then adding ethyl orthosilicate ethanol solution, and performing ultrasonic treatment for 2-4 h at 20-30 ℃ to form a core-shell structure α -Fe2O3@SiO2Step three, the core-shell structure α -Fe obtained in the step two2O3@SiO2Dispersing the composite microspheres into hydrochloric acid, stirring and reacting for 6-12 h to obtain α -Fe2O3@SiO2Hollow composite microsphere, step four, α -Fe obtained in step three2O3@SiO2Calcining hollow composite microspheres in reducing atmosphereWashing, magnetically separating to form bell-shaped structure Fe @ SiO2And (3) compounding the microspheres. The invention has the advantages of controllable structure, high stability, good dispersibility, difficult agglomeration and strong adsorption capacity.
Description
Technical Field
The invention belongs to the field of environment nano materials, and particularly relates to a bell-shaped structure Fe @ SiO2Composite microspheres, a preparation method and application thereof.
Background
Because of its good water quality and stable water supply, groundwater has become an important water source for domestic water, industrial and agricultural irrigation. Once the groundwater is polluted, pollutants can diffuse to aquifers along with the flow of the groundwater, and the safety of human beings, animals and plants is threatened directly or indirectly. Industrial wastewater and domestic sewage are the main pollution sources of groundwater in China. At present, underground water in China is facing the trend of spreading from point to surface, shallow and deep, and from cities to rural areas, and the pollution degree is increasingly aggravated. Among the precious metal pollution of various underground water, such as chromium, arsenic, cadmium, lead and the like, Cr (VI) pollution caused by the massive use, unreasonable discharge and leakage of Cr (VI) in the industry is particularly serious, and Cr (VI) in the underground water of many places in China seriously exceeds the standard.
Cadmium is a natural element and widely exists in soil, animal and plant bodies, volcanic ash and the like. Cr (VI), Cr (III) and Cr (0) are three common forms of chromium. Cr (iii) is produced in nature, is less toxic and less mobile, and is an essential element in the human body. Cr (VI) has strong toxicity, carcinogenic, teratogenic and mutagenic effects, and can be enriched in animals and plants to influence human life and health through food chain. The restoration of hexavalent chromium in groundwater is therefore a serious problem currently facing.
Because the metallic iron has the characteristics of strong reducing capability, high reaction speed, low cost and the like, the application of the metallic iron in removing various pollutants in the environment is a good choice. For groundwater remediation, nanoscale zero-valent iron has obvious advantages in the treatment of environmental pollutants, on one hand, the particles of the nanoscale zero-valent iron are small and easy to flow and migrate in groundwater, and can be suspended and dispersed in a solution for a long time to react with pollutants, so that the nanoscale zero-valent iron can be directly injected into a polluted position to remediate the underground pollutants, and on the other hand, the nanoscale zero-valent iron can be controlled by an external magnetic field, so that the nanoscale zero-valent iron can be treated in a fixed-point oriented mode, and can be rapidly separated and recovered after environmental remediation. However, in practical engineering application, the nano-iron material is easy to agglomerate to form floccules, so that the activity of the floccules is reduced, and the floccules are easy to oxidize in the environment, which greatly limits the in-situ repair capability of the floccules, and is a problem to be solved in preparation and use of the current nano-iron material.
Silicon dioxide is one of the best choices for shell materials due to its characteristics of high melting point, hydrophilicity and insolubility in water, stable chemical properties, simple preparation and the like. The silicon dioxide material is used as an outer shell layer to coat the nano iron material, so that not only can the iron core be protected from being oxidized or corroded, but also the dipole interaction between iron nano particles can be shielded, the particles are prevented from agglomerating, and the suspension characteristic and stability of the core-shell particles in water are improved.
Therefore, the design and preparation of the nano composite material with controllable structure, high stability and good hexavalent chromium repairing performance has very important significance in the field of environmental pollutant treatment.
Disclosure of Invention
The invention aims to provide a simple method for designing and preparing a bell-type structure Fe @ SiO with controllable structure, high stability and good hexavalent chromium repairing performance2Composite microspheres, a preparation method and application thereof.
In order to solve the technical problems, the invention provides a bell-shaped structure Fe @ Si02The preparation method of the composite microsphere comprises the following steps:
step one, adding ferric trichloride into water for dissolving, adding hydrochloric acid, stirring uniformly, and carrying out reaction at the temperature of 100-160 DEG CCarrying out hydrothermal reaction for 12-24 h to obtain α -Fe2O3Nano-microspheres;
step two, α -Fe prepared in step one2O3Dispersing the nano microspheres into 20-98 vol% ethanol according to the solid-to-liquid ratio of 1 g: 60 ml-1 g: 120ml, adding ammonia water, stirring uniformly, then adding ethyl orthosilicate (TEOS) ethanol solution, and performing ultrasonic treatment for 2-4 h at 20-30 ℃ to form a core-shell structure α -Fe2O3@SiO2Compounding the microspheres;
step three, α -Fe obtained in step two2O3@SiO2Dispersing the composite microspheres into hydrochloric acid, stirring and reacting for 6-12 h to obtain α -Fe2O3@SiO2Hollow composite microspheres;
step four, α -Fe obtained in step three2O3@SiO2Calcining the hollow composite microspheres in a reducing atmosphere, washing, and carrying out magnetic separation to form the bell-shaped structure Fe @ SiO2And (3) compounding the microspheres.
Preferably, in the first step, the mass ratio of ferric trichloride to water is 1: 80-1: 20, and the concentration of hydrochloric acid is 10-3-10-2mol/L。
Preferably, the volume fraction of the tetraethoxysilane in the ethanol solution of the tetraethoxysilane in the step two is 0.1-8%; the volume ratio of 20-98 vol% ethanol to ammonia water is 8: 1-16: 1; the concentration of the ammonia water is 3-14.5 mol/L.
Further, in the second step, the volume ratio of 20-98 vol% ethanol to ethyl orthosilicate ethanol solution is 3: 1-12: 1.
Specifically, the concentration of the hydrochloric acid in the third step is 1 mol/L-12 mol/L.
Further, the α -Fe2O3@SiO2The solid-liquid ratio of the composite microspheres to the hydrochloric acid is 1 g: 100 ml-1 g: 1000 ml.
Preferably, the calcination treatment in the fourth step is performed at a temperature of 300 to 600 ℃ for 60 to 180 min.
The invention also comprises a bell-shaped structure Fe @ SiO2Composite microspheres, useAny bell type structure Fe @ SiO prepared by the preparation method2And (3) compounding the microspheres.
Further, the bell-shaped structure Fe @ SiO2The particle size of the shell of the composite microsphere is 240-300nm, and the particle size of the inner core is 44-170 nm.
The invention also comprises a bell-shaped structure Fe @ SiO2The composite microspheres are used for adsorption removal of heavy metals Cr (VI) in underground water.
In particular, with potassium dichromate (K)2Cr2O7) As a chromium source of hexavalent chromium Cr (VI), Cr (VI) ion solutions with different concentrations are prepared, and the pH value of the solution is adjusted to 2.5 by HCl and NaOH. When isothermal adsorption data were measured, the pH of the solution was adjusted to 2.5 at room temperature for each test. 10g of the sample was placed in 40ml of the above chromium ion solution for 12 hours, and then the sample was separated from the solution by an external magnetic field.
The invention has the following beneficial effects:
(1) firstly, α -Fe is prepared by a hydrothermal method2O3The particle size of the nanometer microsphere particle is about 100nm, and the bell-shaped structure α -Fe with controllable appearance is prepared by a simple template method and a solvothermal method under the alkaline condition of ammonia water by taking Tetraethoxysilane (TEOS) as a silicon source2O3@SiO2Composite microsphere, α -Fe corroded by hydrochloric acid2O3@SiO2Compounding the microspheres to obtain α -Fe with bell-shaped structure2O3@SiO2Hollow composite microspheres are calcined by hydrogen to prepare Fe @ SiO with ferromagnetic bell-shaped structure2And (3) compounding the microspheres.
(2) The preparation method is simple and suitable for industrial production, and the prepared bell-shaped structure Fe @ SiO2The composite microsphere has the advantages of controllable structure, high stability, good dispersibility, difficult agglomeration, extremely strong adsorption capacity, wide application in the aspect of energy environment adsorption, easy recovery and reutilization.
(3) The bell-shaped structure of the invention is Fe @ SiO2The composite microspheres particularly show good adsorption removal capability on a chromium source of heavy metal hexavalent chromium Cr (VI).
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which
FIG. 1 shows α -Fe prepared in example 12O3Scanning electron microscopy of the nanospheres;
FIG. 2 shows α -Fe prepared in example 12O3Transmission electron microscopy images of the nanospheres;
FIG. 3 shows α -Fe with core-shell structure prepared in example 12O3@SiO2Transmission electron microscopy of composite microspheres;
FIG. 4 shows the bell-type structure Fe @ SiO prepared in example 12Transmission electron microscopy of composite microspheres;
FIG. 5 shows the bell-type structure Fe @ SiO prepared in example 12XRD pattern of composite microspheres;
FIG. 6 shows the bell-type structure Fe @ SiO prepared in example 12EDAX map of composite microspheres;
FIG. 7 shows the bell-type structure Fe @ SiO prepared in example 12The adsorption isotherm curve of the composite microspheres to Cr (VI);
FIG. 8 shows the bell-shaped structure Fe @ SiO prepared in example 22Transmission electron microscopy of composite microspheres;
FIG. 9 shows the bell type structure Fe @ SiO prepared in example 32Transmission electron microscopy of composite microspheres.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Example 1
Bell type structure Fe @ SiO2The preparation method of the composite microsphere comprises the following steps:
step one, adding a certain amount of ferric trichloride into water for dissolving,adding hydrochloric acid, continuously stirring uniformly, transferring to a mechanical stirring reaction kettle, performing hydrothermal reaction at 100-160 ℃ for 12-24 h, cooling to room temperature, washing the obtained orange red solid with ethanol and water to obtain α -Fe2O3Nano-microspheres;
step two, the Fe prepared in the step one2O3Dispersing the nano microspheres into 92 vol% ethanol according to a solid-liquid ratio of 1 g: 60 ml-1 g: 120m1, adding ammonia water, stirring uniformly, then adding an ethanol solution of tetraethyl orthosilicate (TEOS), performing ultrasonic treatment for 2-4 h at 20-30 ℃, washing the obtained solid with ethanol, then washing with water, and then drying at 55-65 ℃ to obtain the core-shell structure α -Fe2O3@SiO2Compounding the microspheres;
step three, the Fe obtained in the step two2O3@SiO2Dispersing the composite microspheres into hydrochloric acid, stirring for reaction for 6-12 h, centrifugally separating the obtained solid, washing with ethanol and water, and drying at 55-65 ℃ to obtain α -Fe2O3@SiO2Hollow composite microspheres;
step four, α -Fe obtained in step three2O3@SiO2Calcining the hollow composite microspheres in a reducing atmosphere, cooling to room temperature, washing with ethanol and water, performing magnetic separation, and drying to obtain black powder, namely bell-shaped structure Fe @ SiO2And (3) compounding the microspheres.
Specifically, in the first step, the mass ratio of ferric trichloride to water is 1: 40, and the concentration of hydrochloric acid is 10-3mol/L。
Further, the volume fraction of TEOS in the ethanol solution of TEOS in the second step is 2%; the volume ratio of the 92 vol% ethanol to the ammonia water is 12: 1; the concentration of the ammonia water is 8 mol/L; preferably, the volume ratio of the 92 vol% ethanol to the TEOS ethanol solution is 6: 1.
Preferably, the concentration of the hydrochloric acid in the step three is 8mol/L, α -Fe2O3@SiO2The solid-liquid ratio of the composite microspheres to the hydrochloric acid is 1g to 200 ml.
Further, the bell-shaped structure α -Fe in the fourth step2O3@SiO2The composite microspheres are kept for 120min at 500 ℃ under hydrogen atmosphere.
Characterization test α -Fe prepared in example 12O3The scanning electron microscopy image of the nanospheres is shown in FIG. 1, and it can be seen from FIG. 1 that α -Fe2O3The nano-microspheres are regularly arranged and have good dispersibility, and α -Fe prepared in example 12O3The transmission electron microscopy image of the nano-microsphere is shown in FIG. 2, and it can be seen from FIG. 2 that the nano-microsphere has a size of about 100nm and a large amount of α -Fe2O3Composition of nanoparticles, core-shell structure α -Fe prepared in example 12O3@SiO2The transmission electron microscope image of the composite microsphere is shown in FIG. 3. from FIG. 3, it can be seen that SiO2Successful coating with Fe2O3Surface of nano-microsphere, SiO2Has a thickness of about 15nm and is coated with SiO2Good monodispersity is still kept after the shell layer; bell-type structure Fe @ SiO prepared in example 12The transmission electron microscopy image of the composite microsphere is shown in FIG. 4, and as can be seen from FIG. 4, the core-shell structure is α -Fe2O3@SiO2The composite microspheres are corroded by 8mol/L hydrochloric acid and calcined to form bell-shaped structure Fe @ SiO2Composite microspheres of SiO2The integrity of the shell layer is still kept, in the embodiment, the bell-shaped structure Fe @ SiO2The composite microsphere has the average particle size of the shell of 265nm and the average particle size of the inner core of 48 nm; bell-type structure Fe @ SiO prepared in example 12The XRD pattern of the composite microspheres is shown in FIG. 5. from FIG. 5, it can be seen that the 2 θ curve at 30 ° shows significant SiO2The characteristic peak of (A) shows a stronger characteristic peak of Fe at 45 degrees, which indicates α -Fe after the calcination treatment in the tube furnace2O3@SiO2Compound microsphere is converted into ferromagnetic bell-shaped structure Fe @ SiO2And (3) compounding the microspheres. Bell-type structure Fe @ SiO prepared in example 12The EDAX diagram of the composite microsphere is shown in FIG. 5, and as can be seen from FIG. 6, the spectrum has obvious Fe, O and Si elements.
Bell type structure Fe @ SiO2The composite microspheres are used for adsorption removal of heavy metals Cr (VI) in underground water. Bell prepared in example 1Type structure Fe @ SiO2Adsorption removal test of composite microspheres on heavy metal Cr (VI) with potassium dichromate (K)2Cr2O7) As a chromium source of hexavalent chromium Cr (VI), Cr (VI) ion solutions with different concentrations are prepared, and the pH value of the solution is adjusted to 2.5 by HCl and NaOH. When isothermal adsorption data were measured, the pH of the solution was adjusted to 2.5 at room temperature for each test. 10g of the sample was placed in 40ml of the above chromium ion solution for 12 hours, and then the sample was separated from the solution by an external magnetic field. With reference to FIG. 7, the bell-type structure Fe @ SiO prepared in example 12The isothermal adsorption curve of the composite microspheres on Cr (VI) is shown, and the isothermal adsorption curve is Fe @ SiO due to the bell-shaped structure2Special structure of composite microsphere, prepared bell type structure Fe @ SiO2The maximum adsorption capacity of the composite microspheres on Cr (VI) is up to 261.18mg/g, and the composite microspheres can be applied to adsorption removal of heavy metals Cr (VI) in underground water.
Example 2
Bell type structure Fe @ SiO2The preparation method of the composite microsphere comprises the following steps:
step one, adding a certain amount of ferric trichloride into water to dissolve, adding hydrochloric acid, continuously stirring uniformly, transferring into a mechanical stirring reaction kettle, carrying out hydrothermal reaction for 12-24 h at 100-160 ℃, cooling to room temperature, washing obtained orange red solid with ethanol and water to obtain α -Fe2O3Nano-microspheres;
step two, the Fe prepared in the step one2O3Dispersing the nano microspheres into 92 vol% ethanol according to a solid-to-liquid ratio of 1 g: 60 ml-1 g: 120ml, adding ammonia water, uniformly stirring, then adding an ethanol solution of tetraethyl orthosilicate (TEOS), performing ultrasonic treatment at 20-30 ℃ for 2-4 h, washing the obtained solid with ethanol, then washing with water, and then drying at 55-65 ℃ to obtain α -Fe with a core-shell structure2O3@SiO2Compounding the microspheres;
step three, the Fe obtained in the step two2O3@SiO2Dispersing the composite microspheres into hydrochloric acid, stirring for reaction for 6-12 h, centrifugally separating the obtained solid, washing with ethanol and water, and drying at 55-65 ℃ to obtain α -Fe2O3@SiO2Hollow composite microspheres;
step four, α -Fe obtained in step three2O3@SiO2Calcining the hollow composite microspheres in a reducing atmosphere, cooling to room temperature, washing with ethanol and water, performing magnetic separation, and drying to obtain black powder, namely bell-shaped structure Fe @ SiO2And (3) compounding the microspheres.
Specifically, in the first step, the mass ratio of ferric trichloride to water is 1: 60, and the concentration of hydrochloric acid is 5 x 10-3mol/L。
Further, the volume fraction of TEOS in the ethanol solution of TEOS in the second step is 4%; the volume ratio of the 92 vol% ethanol to the ammonia water is 12: 1; the concentration of the ammonia water is 8 mol/L; the volume ratio of the 92 vol% ethanol to the TEOS ethanol solution is 6: 1.
Preferably, the concentration of the hydrochloric acid in the step three is 2mol/L, α -Fe2O3@SiO2The solid-liquid ratio of the composite microspheres to the hydrochloric acid is 1g to 200 ml.
Further, the step four bell type structure α -Fe2O3@SiO2The composite microspheres are kept for 100min at 400 ℃ under hydrogen atmosphere.
α -Fe prepared in example 22O3FIG. 8 shows a scanning electron microscope image of the nanospheres, and FIG. 8 shows that in this embodiment, the bell-shaped structure Fe @ SiO2The composite microsphere has an average shell particle size of 261nm and an inner core particle size of 149 nm. The controllable preparation of the structure and the size of the cavity is realized by regulating and controlling preparation parameters.
Example 3
Bell type structure Fe @ SiO2The preparation method of the composite microsphere comprises the following steps:
step one, adding a certain amount of ferric trichloride into water to dissolve, adding hydrochloric acid, continuously stirring uniformly, transferring into a mechanical stirring reaction kettle, carrying out hydrothermal reaction for 12-24 h at 100-160 ℃, cooling to room temperature, washing obtained orange red solid with ethanol and water to obtain α -Fe2O3Nano-microspheres;
step two, the Fe prepared in the step one2O3Dispersing the nano microspheres into 92 vol% ethanol according to a solid-to-liquid ratio of 1 g: 60 ml-1 g: 120ml, adding ammonia water, uniformly stirring, then adding an ethanol solution of tetraethyl orthosilicate (TEOS), performing ultrasonic treatment at 20-30 ℃ for 2-4 h, washing the obtained solid with ethanol, then washing with water, and then drying at 55-65 ℃ to obtain α -Fe with a core-shell structure2O3@SiO2Compounding the microspheres;
step three, the Fe obtained in the step two2O3@SiO2Dispersing the composite microspheres into hydrochloric acid, stirring for reaction for 6-12 h, centrifugally separating the obtained solid, washing with ethanol and water, and drying at 55-65 ℃ to obtain α -Fe2O3@SiO2Hollow composite microspheres;
step four, α -Fe obtained in step three2O3@SiO2Calcining the hollow composite microspheres in a reducing atmosphere, cooling to room temperature, washing with ethanol and water, performing magnetic separation, and drying to obtain black powder, namely bell-shaped structure Fe @ SiO2And (3) compounding the microspheres.
Specifically, in the first step, the mass ratio of ferric trichloride to water is 1: 30, and the concentration of hydrochloric acid is 10-3。
Further, the volume fraction of TEOS in the ethanol solution of TEOS in the second step is 2%; the volume ratio of the 92 vol% ethanol to the ammonia water is 12: 1; the concentration of the ammonia water is 8 mol/L; preferably, the volume ratio of the 92 vol% ethanol to the TEOS ethanol solution is 6: 1.
Preferably, the concentration of the hydrochloric acid in the step three is 6mol/L, α -Fe2O3@SiO2The solid-liquid ratio of the composite microspheres to the hydrochloric acid is 1g to 200 ml.
Further, the bell-shaped structure α -Fe in the fourth step2O3@SiO2The composite microspheres are kept for 120min at 500 ℃ under hydrogen atmosphere.
α -Fe prepared in example 32O3FIG. 9 shows the scanning electron microscope image of the nanospheres, and FIG. 1 shows that in this embodiment, the bell-shaped structure Fe @ SiO2Composite microspheres with a shellThe average particle diameter is 277nm, and the average particle diameter of the inner core is 93 nm.
The invention can further regulate and control the adsorption performance of the composite microsphere on Cr (VI) by controlling the particle size of the Fe core of the cavity, thereby meeting different requirements.
Example 4:
step one, adding a certain amount of ferric trichloride into water to dissolve, adding hydrochloric acid, continuously stirring uniformly, transferring into a mechanical stirring reaction kettle, carrying out hydrothermal reaction for 12h at 100 ℃, cooling to room temperature, washing the obtained orange-red solid with ethanol and water to obtain α -Fe2O3Nano-microspheres;
step two, the Fe prepared in the step one2O3Dispersing the nano-microspheres into 20 vol% ethanol according to a solid-to-liquid ratio of 1 g: 60ml, adding ammonia water, stirring uniformly, then adding an ethanol solution of tetraethyl orthosilicate (TEOS), carrying out ultrasonic treatment at 20-30 ℃ for 2h, washing the obtained solid with ethanol, then washing with water, and then drying at 55-65 ℃ to obtain α -Fe with a core-shell structure2O3@SiO2Compounding the microspheres;
step three, the Fe obtained in the step two2O3@SiO2Dispersing the composite microspheres into hydrochloric acid, stirring for reaction for 6 hours, centrifugally separating the obtained solid, washing with ethanol and water, and drying at 55-65 ℃ to obtain α -Fe2O3@SiO2Hollow composite microspheres;
step four, α -Fe obtained in step three2O3@SiO2Calcining the hollow composite microspheres in a reducing atmosphere, cooling to room temperature, washing with ethanol and water, performing magnetic separation, and drying to obtain black powder, namely bell-shaped structure Fe @ SiO2And (3) compounding the microspheres.
Specifically, in the first step, the mass ratio of ferric trichloride to water is 1: 80, and the concentration of hydrochloric acid is 10-3mol/L。
Further, the volume fraction of the TEOS in the ethanol solution of the TEOS in the second step is 0.1%; the volume ratio of 20 vol% ethanol to ammonia water is 8: 1; the concentration of the ammonia water is 3 mol/L; preferably, the volume ratio of 20 vol% ethanol to TEOS in ethanol is 6: 1.
Preferably, the concentration of the hydrochloric acid in the step three is 1mol/L, α -Fe2O3@SiO2The solid-liquid ratio of the composite microspheres to the hydrochloric acid is 1g to 100 ml.
Further, the bell-shaped structure α -Fe in the fourth step2O3@SiO2The composite microspheres are kept for 60min at 300 ℃ under hydrogen atmosphere.
Example 5:
bell type structure Fe @ SiO2The preparation method of the composite microsphere comprises the following steps:
step one, adding a certain amount of ferric trichloride into water to dissolve, adding hydrochloric acid, continuously stirring uniformly, transferring into a mechanical stirring reaction kettle, carrying out hydrothermal reaction for 24 hours at 160 ℃, cooling to room temperature, washing the obtained orange-red solid with ethanol and water to obtain α -Fe2O3Nano-microspheres;
step two, the Fe prepared in the step one2O3Dispersing the nano-microspheres into 98 vol% ethanol according to the solid-to-liquid ratio of 1 g: 120ml, adding ammonia water, stirring uniformly, then adding an ethanol solution of tetraethyl orthosilicate (TEOS), carrying out ultrasonic treatment at 30 ℃ for 4h, washing the obtained solid with ethanol, then washing with water, and then drying at 55-65 ℃ to obtain α -Fe with the core-shell structure2O3@SiO2Compounding the microspheres;
step three, the Fe obtained in the step two2O3@SiO2Dispersing the composite microspheres into hydrochloric acid, stirring for reaction for 12 hours, centrifugally separating the obtained solid, washing with ethanol and water, and drying at 55-65 ℃ to obtain α -Fe2O3@SiO2Hollow composite microspheres;
step four, α -Fe obtained in step three2O3@SiO2Calcining the hollow composite microspheres in a reducing atmosphere, cooling to room temperature, washing with ethanol and water, performing magnetic separation, and drying to obtain black powder, namely bell-shaped structure Fe @ SiO2And (3) compounding the microspheres.
Specifically, in the step one, the mass ratio of ferric trichloride to water is 1: 20, and the salt isThe acid concentration is 10-2mol/L。
Further, the volume fraction of TEOS in the ethanol solution of TEOS in the second step is 8%; the volume ratio of 98 vol% ethanol to ammonia water is 16: 1; the concentration of the ammonia water is 14.5 mol/L; preferably, the volume ratio of 98 vol% ethanol to TEOS in ethanol is 12: 1.
Preferably, the concentration of the hydrochloric acid in the step three is 12mol/L, α -Fe2O3@SiO2The solid-liquid ratio of the composite microspheres to the hydrochloric acid is 1 g: 1000 ml.
Further, the bell-shaped structure α -Fe in the fourth step2O3@SiO2The composite microspheres are kept for 180min at 600 ℃ under hydrogen atmosphere.
Example 6:
bell type structure Fe @ SiO2The preparation method of the composite microsphere comprises the following steps:
step one, adding a certain amount of ferric trichloride into water to dissolve, adding hydrochloric acid, continuously stirring uniformly, transferring into a mechanical stirring reaction kettle, carrying out hydrothermal reaction for 18h at 120 ℃, cooling to room temperature, washing the obtained orange-red solid with ethanol and water to obtain α -Fe2O3Nano-microspheres;
step two, the Fe prepared in the step one2O3Dispersing the nano microspheres into 75 vol% ethanol according to the solid-to-liquid ratio of 1 g: 60 ml-1 g: 120ml, adding ammonia water, stirring uniformly, then adding an ethanol solution of tetraethyl orthosilicate (TEOS), performing ultrasonic treatment at 30 ℃ for 3 hours, washing the obtained solid with ethanol, then washing with water, and then drying at 55-65 ℃ to obtain α -Fe with a core-shell structure2O3@SiO2Compounding the microspheres;
step three, the Fe obtained in the step two2O3@SiO2Dispersing the composite microspheres into hydrochloric acid, stirring for reaction for 9 hours, centrifugally separating the obtained solid, washing with ethanol and water, and drying at 55-65 ℃ to obtain α -Fe2O3@SiO2Hollow composite microspheres;
step four, α -Fe obtained in step three2O3@SiO2Calcining the hollow composite microspheres in a reducing atmosphere, cooling to room temperature, washing with ethanol and water, performing magnetic separation, and drying to obtain black powder, namely bell-shaped structure Fe @ SiO2And (3) compounding the microspheres.
Specifically, in the first step, the mass ratio of ferric trichloride to water is 1: 60, and the concentration of hydrochloric acid is 8 x 10-3mol/L。
Further, the volume fraction of TEOS in the ethanol solution of TEOS in the second step is 4%; the volume ratio of the 75 vol% ethanol to the ammonia water is 10: 1; the concentration of the ammonia water is 12 mol/L; preferably, the volume ratio of the 75 vol% ethanol to the TEOS ethanol solution is 9: 1.
Preferably, the concentration of the hydrochloric acid in the step three is 4mol/L, α -Fe2O3@SiO2The solid-liquid ratio of the composite microspheres to the hydrochloric acid is 1 g: 800 ml.
Further, the bell-shaped structure α -Fe in the fourth step2O3@SiO2The composite microspheres are kept for 150min at 400 ℃ under hydrogen atmosphere.
Example 7:
bell type structure Fe @ SiO2Composite microspheres prepared according to examples 1-5, Fe @ SiO2The particle size of the shell of the composite microsphere is 240-300nm, and the particle size of the inner core is 44-170 nm. As shown in FIG. 4, the bell type structure Fe @ SiO prepared in example 12The composite microsphere has the average particle size of the shell of 265nm and the average particle size of the inner core of 48 nm; as shown in FIG. 8, the bell type structure Fe @ SiO prepared in example 22The composite microsphere has an average shell particle size of 261nm and an inner core particle size of 149 nm; as shown in FIG. 9, the bell type structure Fe @ SiO prepared in example 32The average grain diameter of the shell of the composite microsphere is 277nm, and the average grain diameter of the inner core of the composite microsphere is 93 nm.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (7)
1. Bell type structure Fe @ SiO2The preparation method of the composite microspheres is characterized by comprising the following steps:
step one, adding ferric trichloride into water for dissolving, adding hydrochloric acid, stirring uniformly, and carrying out hydrothermal reaction for 12-24 h at 100-160 ℃ to obtain α -Fe2O3Nano-microspheres;
step two, α -Fe prepared in step one2O3Dispersing the nano microspheres into 20-98 vol% ethanol according to the solid-to-liquid ratio of 1 g: 60 ml-1 g: 120ml, adding ammonia water, stirring uniformly, then adding ethyl orthosilicate ethanol solution, and performing ultrasonic treatment for 2-4 h at 20-30 ℃ to form a core-shell structure α -Fe2O3@SiO2Compounding the microspheres;
step three, the core-shell structure α -Fe obtained in the step two2O3@SiO2Dispersing the composite microspheres into hydrochloric acid, stirring and reacting for 6-12 h to obtain α -Fe2O3@SiO2Hollow composite microspheres;
step four, α -Fe obtained in step three2O3@SiO2Calcining the hollow composite microspheres in a reducing atmosphere, washing, and carrying out magnetic separation to form the bell-shaped structure Fe @ SiO2Compounding the microspheres;
in the first step, the mass ratio of ferric trichloride to water is 1: 80-1: 20, and the concentration of hydrochloric acid is 10-3-10-2mol/L; in the second step, the volume fraction of the tetraethoxysilane in the ethanol solution of the tetraethoxysilane is 0.1-8%; the volume ratio of 20-98 vol% ethanol to ammonia water is 8: 1-16: 1; the concentration of the ammonia water is 3-14.5 mol/L;
the third step of the core-shell structure α -Fe2O3@SiO2The solid-liquid ratio of the composite microspheres to the hydrochloric acid is 1 g: 100 ml-1 g: 1000 ml.
2. The bell type structure of claim 1 Fe @ SiO2A preparation method of a composite microsphere, which comprises the following steps of,the method is characterized in that the volume ratio of 20-98 vol% ethanol to ethyl orthosilicate ethanol solution in the second step is 3: 1-12: 1.
3. The bell type structure of claim 1 Fe @ SiO2The preparation method of the composite microspheres is characterized in that the concentration of hydrochloric acid in the step three is 1-12 mol/L.
4. The bell type structure of claim 1 Fe @ SiO2The preparation method of the composite microspheres is characterized in that the reducing atmosphere in the fourth step is hydrogen, and the calcination treatment is carried out for 60-180 min at the temperature of 300-600 ℃.
5. Bell type structure Fe @ SiO2Composite microspheres characterized in that they are made of Fe @ SiO in a bell-type structure by the process of any one of claims 1 to 42And (3) compounding the microspheres.
6. The bell type structure of claim 5 Fe @ SiO2The composite microsphere is characterized in that the bell-shaped structure Fe @ SiO2The particle size of the shell of the composite microsphere is 240-300nm, and the particle size of the inner core is 44-170 nm.
7. The bell-type structure of any claim 5-6 Fe @ SiO2The composite microspheres are used for adsorption removal of heavy metals Cr (VI) in underground water.
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Application publication date: 20171107 Assignee: Taizhou Runhe New Material Technology Co.,Ltd. Assignor: ZHEJIANG SCI-TECH University Contract record no.: X2024330000360 Denomination of invention: A bell shaped structure Fe@SiO2Composite microspheres, preparation methods, and applications Granted publication date: 20200407 License type: Common License Record date: 20240806 Application publication date: 20171107 Assignee: Zhejiang Jusheng New Material Technology Co.,Ltd. Assignor: ZHEJIANG SCI-TECH University Contract record no.: X2024330000359 Denomination of invention: A bell shaped structure Fe@SiO2Composite microspheres, preparation methods, and applications Granted publication date: 20200407 License type: Common License Record date: 20240806 Application publication date: 20171107 Assignee: Taizhou Yiguan New Material Technology Co.,Ltd. Assignor: ZHEJIANG SCI-TECH University Contract record no.: X2024330000358 Denomination of invention: A bell shaped structure Fe@SiO2Composite microspheres, preparation methods, and applications Granted publication date: 20200407 License type: Common License Record date: 20240806 Application publication date: 20171107 Assignee: Taizhou Henghong New Materials Co.,Ltd. Assignor: ZHEJIANG SCI-TECH University Contract record no.: X2024330000357 Denomination of invention: A bell shaped structure Fe@SiO2Composite microspheres, preparation methods, and applications Granted publication date: 20200407 License type: Common License Record date: 20240806 |